Chloroiodomethane → HCID 22598017, compound

HRID 2184961Notes

Reaction equation

HRID 2184961 reaction equation
[CH:1]([O:3][C:4]1[CH:5]=[C:6]([CH2:14][O:15][Si:16]([CH:23]([CH3:25])[CH3:24])([CH:20]([CH3:22])[CH3:21])[CH:17]([CH3:19])[CH3:18])[CH:7]=[CH:8][C:9]=1[O:10][CH:11]([F:13])[F:12])=[CH2:2].Cl[CH2:27]I.C([Zn]CC)C>ClCCl>[CH:1]1([O:3][C:4]2[CH:5]=[C:6]([CH2:14][O:15][Si:16]([CH:17]([CH3:18])[CH3:19])([CH:23]([CH3:25])[CH3:24])[CH:20]([CH3:22])[CH3:21])[CH:7]=[CH:8][C:9]=2[O:10][CH:11]([F:12])[F:13])[CH2:27][CH2:2]1

Participants

5

Reactant 3

HCID 11644ChloroiodomethaneHCID 22598003HCID 22598003, compoundHCID 178418750HCID 178418750, compound

Product 1

HCID 22598017HCID 22598017, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
5 °C

Procedure

To a solution of the alkene, 3-Ethenyloxy-4-difluoromethoxy-1-(triisopropylsilyloxy)methylbenzene, from Step 3 (67 g, 179 mmol) and chloroiodomethane (78 mL, 1.07 mol) in dichloromethane (1.5 L) at 5° C. (ice bath) was added diethyl zinc (55 mL, 537 mmol) in 5 mL portions over 1.2 h. During the addition, the internal temperature was maintained at <20° C. After the addition was complete, the mixture was stirred for 15 min and then the cooling bath was removed and stirring was continued for a further 2.5 h. The mixture was re-cooled to 5° C. (ice bath) and MeOH (2 mL) was added over 15 min, followed by the addition of water (30 mL) over 15 min and finally, the addition of 6N HCl (5 mL). The mixture was partitioned between ether (1 L) and water (500 mL). The aqueous layer was extracted with ether (500 mL) and the combined organics were washed with brine, dried (Na2SO4) and concentrated. Flash chromatography of the residue (silica gel; hexane/ethyl acetate 98:2 to 95:5) provided 3-Cyclopropyloxy-4-difluoromethoxy-1-(triisopropylsilyloxy)methylbenzene (71 g).

Workup

  1. additionDuring the addition
  2. temperaturethe internal temperature was maintained at <20° C
  3. additionAfter the addition
  4. customthe cooling bath was removed
  5. stirringstirring
  6. waitwas continued for a further 2.5 h
  7. additionwas added over 15 min
  8. additionfollowed by the addition of water (30 mL) over 15 min
  9. additionfinally, the addition of 6N HCl (5 mL)
  10. customThe mixture was partitioned between ether (1 L) and water (500 mL)
  11. extractionThe aqueous layer was extracted with ether (500 mL)
  12. washthe combined organics were washed with brine
  13. dry with materialdried (Na2SO4)
  14. concentrationconcentrated

Sources & evidence

ORD record
ord-bf3073ba264844779e56f7a5c9b54597
Source dataset
uspto-grants-2002_06
Patent number
US06399636B2

Reaction notes

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